WO2021100735A1 - Matériau composite et son procédé de production - Google Patents

Matériau composite et son procédé de production Download PDF

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Publication number
WO2021100735A1
WO2021100735A1 PCT/JP2020/042901 JP2020042901W WO2021100735A1 WO 2021100735 A1 WO2021100735 A1 WO 2021100735A1 JP 2020042901 W JP2020042901 W JP 2020042901W WO 2021100735 A1 WO2021100735 A1 WO 2021100735A1
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Prior art keywords
fiber
cnt
resin
composite material
cnts
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PCT/JP2020/042901
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English (en)
Japanese (ja)
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拓治 小向
麻季 鬼塚
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ニッタ株式会社
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Application filed by ニッタ株式会社 filed Critical ニッタ株式会社
Priority to US17/778,164 priority Critical patent/US20230019296A1/en
Priority to CN202080079115.8A priority patent/CN114729499A/zh
Priority to EP20891341.8A priority patent/EP4063559A4/fr
Priority to KR1020227020334A priority patent/KR20220093248A/ko
Priority to JP2021558473A priority patent/JPWO2021100859A1/ja
Priority to TW109140794A priority patent/TW202124808A/zh
Priority to PCT/JP2020/043412 priority patent/WO2021100859A1/fr
Publication of WO2021100735A1 publication Critical patent/WO2021100735A1/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts

Definitions

  • the present invention relates to a composite material and a method for producing the same.
  • a composite material having a structure composed of fibers and a plurality of carbon nanotubes (hereinafter referred to as CNTs) adhering to the surface of the fibers has been proposed (for example, Patent Document 1).
  • the structure of the composite material forms a network structure in which a plurality of CNTs are connected to each other and is attached to the surface of the fiber.
  • a fiber-reinforced plastic body reinforced with a resin using such a composite material as a reinforcing fiber can obtain higher strength and rigidity than a resin alone by containing the fiber, and is derived from CNT, and has electrical conductivity, thermal conductivity, and machinery. Characteristics are improved.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composite material derived from CNT attached to a fiber and capable of further enhancing the characteristics, and a method for producing the same.
  • the composite material of the present invention is composed of fibers and a plurality of carbon nanotubes to form a network structure in which the carbon nanotubes are in direct contact with each other, and the carbon nanotubes adhering to the surface of the fibers are directly attached to the surface of the fibers.
  • the carbon nanotube is provided with an attached structure and has a bent shape having a bent portion.
  • the method for producing a composite material of the present invention includes an ultrasonic step of applying ultrasonic vibration to a dispersion liquid in which a plurality of curved carbon nanotubes having a bent portion are dispersed, and the above-mentioned method in which the ultrasonic vibration is applied. It has a bonding step of immersing continuous fibers in a dispersion liquid, adhering the plurality of carbon nanotubes to the fibers, and forming a structure on the surface of the fibers.
  • the carbon nanotubes attached to the fibers have a bent shape having a bent portion, the number of carbon nanotubes attached to the fibers is increased, and the characteristics derived from the carbon nanotubes are further enhanced. be able to.
  • a composite material is produced by adhering curved carbon nanotubes having bent portions to the surface of the fiber, which has a structure woven like a fiber of a non-woven fabric. Therefore, carbon adhering to the fiber.
  • the number of nanotubes can be increased, and a composite material having more enhanced properties derived from carbon nanotubes can be produced.
  • the composite material 10 includes fibers 11 and a structure 12 formed on the surface of the fibers 11.
  • the structure 12 is formed by entwining a plurality of carbon nanotubes (hereinafter referred to as CNTs) 14.
  • the composite material 10 may be, for example, a fiber in which the structure 12 is impregnated with a resin or the like (hereinafter referred to as a resin-impregnated fiber), or may be used as a single yarn constituting a multifilament or a reinforcing fiber of a fiber-reinforced molded body. ..
  • the composite material 10, the resin-impregnated fiber, the multifilament, the fiber-reinforced molded product, and the like (hereinafter, these are referred to as secondary products) produced by using the composite material 10 have a structure 12 on the surface of the fiber 11.
  • the mechanical properties and the like are improved. That is, the mechanical properties and the like are improved due to the CNT 14 adhering to the surface of the fiber 11.
  • the multifilament 15 has a plurality of composite materials 10 and a matrix resin 16.
  • a multifilament 15 composed of six composite materials 10 is drawn, but the number of composite materials 10 is not particularly limited, and for example, the multifilament 15 is composed of thousands to hundreds of thousands. You can also do it. Further, a plurality of composite materials 10 can be twisted together to form one multifilament 15.
  • the matrix resin 16 for example, a resin such as polyurethane or an elastomer such as synthetic rubber can be used.
  • the matrix resin 16 is interposed between the composite materials 10 to bond the composite materials 10 to each other. This matrix resin is impregnated into the structure 12 of each composite material 10 and cured.
  • the fiber 11 is not particularly limited, and examples thereof include resin fibers such as nylon, polyester, vinylon, and acrylic, glass fibers, and mineral fibers.
  • the diameter of the fiber 11 is also not particularly limited, and those having a diameter in the range of 5 ⁇ m or more and 100 ⁇ m or less can be preferably used, and those having a diameter in the range of 5 ⁇ m or more and 30 ⁇ m or less can be more preferably used.
  • a long fiber 11 is used, and the length thereof is preferably 50 m or more, more preferably 100 m or more and 100,000 m or less, and further preferably 100 m or more and 10000 m or less.
  • the fibers 11 may be cut short after the structure 12 is formed.
  • the CNTs 14 constituting the structure 12 are evenly dispersed and entangled on almost the entire surface of the fibers 11 to form a network structure in which a plurality of CNTs 14 are connected to each other in an entangled state.
  • the connection here includes a physical connection (mere contact) and a chemical connection.
  • the CNTs 14 are in direct contact with each other without the presence of a dispersant such as a surfactant or an inclusion such as an adhesive between them.
  • some CNTs 14 constituting the structure 12 are directly attached and fixed to the surface of the fiber 11.
  • the structure 12 is directly attached to the surface of the fiber 11.
  • the fact that the CNT 14 directly adheres to the surface of the fiber 11 means that the CNT 14 directly adheres to the fiber 11 without any dispersant such as a surfactant or an adhesive intervening between the CNT 14 and the surface. Yes, the adhesion (fixation) is due to the bond by Van der Waals force. Since some of the CNTs 14 constituting the structure 12 are directly attached to the surface of the fiber 11, the structure 12 comes into direct contact with the surface of the fiber 11 without the intervention of a dispersant or an adhesive. It is in contact.
  • the CNT14 As the CNT14, a bent shape is used. As a result, some CNTs 14 constituting the structure 12 are fixed to the fibers 11 by being entangled with other CNTs 14 without directly contacting the surface of the fibers 11. Further, there are some that are directly attached to the surface of the fiber 11 and are fixed to the fiber 11 by being entangled with other CNTs 14. Hereinafter, the fixation of the CNT 14 to the fiber 11 will be collectively referred to as attachment to the fiber 11.
  • the state in which the CNT 14 is entangled or entangled includes a state in which a part of the CNT 14 is pressed against another CNT 14.
  • the CNT 14 constituting the structure 12 is fixed to the fiber 11 by being entangled with another CNT 14 although it is not in direct contact with the surface of the fiber 11 in addition to directly adhering to the surface of the fiber 11 as described above.
  • the structure 12 of this example is composed of more CNTs 14 than the CNTs directly attached to the surface of the fiber as in the conventional composite material structure. That is, the number of CNTs 14 attached to the fibers 11 is larger than that of the conventional one, and the thickness of the structure 12 is also larger than that of the conventional one.
  • the composite material 10 exhibits the performance of electrical conductivity and thermal conductivity derived from CNTs. To do. Further, since the CNT 14 is attached to the surface of the fiber 11 without any inclusions, the CNT 14 constituting the structure 12 is difficult to be peeled off from the surface of the fiber 11, and the composite material 10 and the secondary product containing the composite material 10 are the same. Mechanical strength is improved. Moreover, since the structure 12 has a large thickness, the above-mentioned mechanical strength is further improved. Therefore, even if the fiber 11 has a large diameter, the composite material 10 and the secondary product having improved mechanical strength can be obtained. In the following, the case of the fiber-reinforced molded product as the secondary product will be described, but the same applies to the case of the resin-impregnated fiber and the multifilament.
  • a fiber bundle composed of a plurality of composite materials 10 on which a structure 12 is formed is impregnated with a matrix resin and cured. Since the matrix resin of the fiber-reinforced molded product is impregnated into the structure 12 and cured, the structure 12 of each composite material 10 is fixed to the matrix resin together with the surface of the fiber 11. As a result, each fiber 11 is firmly adhered to the matrix resin, and the peel strength between the composite material 10 and the matrix resin is improved. Further, since the adhesion with the matrix resin extends over the entire composite material 10, the effect of fiber reinforcement can be obtained in the entire fiber reinforced molded product.
  • each fiber 11 in the fiber reinforced molded body there is a region (hereinafter referred to as a composite region) formed by impregnating the CNT 14 constituting the structure 12 with the matrix resin and curing it as described above. Since the structure 12 has CNTs 14 floating from its surface, the concentration (density) of CNTs 14 in the composite region decreases as the distance from the composite material 10 increases. In such a composite region, the CNT 14 and the matrix resin are composited to have high strength and flexibility derived from the CNT 14. Further, such a composite region provides an effect of relaxing stress concentration, a restraining effect of suppressing displacement of the composite material 10, an effect of efficiently absorbing mechanical energy from the outside, and the like.
  • the vibration damping characteristic (vibration damping property) of the fiber-reinforced molded product is improved.
  • the fibers 11 inside the fiber-reinforced molded product are displaced.
  • the displacement of the fiber 11 causes the structure 12 in the composite region to stretch, and the network structure of the CNT 14 provides a restraining effect.
  • the characteristics of CNT 14 are exhibited and the elastic modulus of the fiber-reinforced molded product is increased.
  • the characteristics derived from CNT14 of the fiber-reinforced molded product are exhibited by the properties of the composite region as described above, the effect of the composite region, and the like.
  • the structure 12 has a structure in which the number of CNTs 14 attached to the fibers 11 is increased and the CNTs 14 are woven like fibers of a non-woven fabric, so that a composite structure such as the structure 12 is not formed.
  • the properties derived from the CNT of the fiber-reinforced molded body are high.
  • the structures 12 formed in the plurality of composite materials 10 are independent of each other, and the structure 12 of one composite material 10 and the structure 12 of the other composite material 10 do not share the same CNT 14. .. That is, the CNT 14 included in the structure 12 provided on one fiber 11 is not included in the structure 12 provided on the other fiber 11.
  • a sizing agent (not shown) is fixed to the surface of the CNT 14 constituting the structure 12.
  • This sizing agent comprises a cured or uncured product of a reaction-curable resin, a thermosetting resin, or a thermoplastic resin.
  • the sizing agent is formed by subjecting it to a sizing treatment.
  • the sizing agent covers the surface of the CNTs 14, and at the contacting portion where the CNTs 14 are in contact with each other, an inclusion portion that wraps and covers the contacting portion is formed.
  • This inclusion portion makes the state in which the CNTs 14 are in contact with each other stronger, and makes the structure 12 more difficult to collapse.
  • the sizing agent is fixed to each CNT 14 in a state where it does not enter between the CNTs 14 that are in contact with each other, so that the CNTs 14 at the contact portion are in direct contact with each other.
  • a plurality of CNTs 14 form a gap (mesh) surrounding the gap, but the sizing agent fills the gap so as not to prevent the structure 12 from being impregnated with the matrix resin. It is preferable not to block it.
  • the volume of the sizing agent is preferably 30% or less with respect to the volume of CNT 14 of the structure 12.
  • the sizing agent is formed on the surface of the CNT 14, and is different from the fixing resin portion described later, which enters the inside of the structure 12 and fixes the CNT 14 to the fiber 11.
  • the CNT 14 attached to the fiber 11 has a bent shape.
  • the curved shape of the CNT 14 is due to having a bent portion (bent portion) due to the presence of a five-membered ring and a seven-membered ring in the graphite structure of the CNT 14, and the CNT 14 is curved as observed by SEM. It is a shape that can be evaluated as being bent.
  • the curved shape of the CNT 14 means that there are at least one bent portion per the average length of the range of use described later of the CNT 14.
  • the curved CNT 14 adheres to the surface of the curved fiber 11 in various postures even if it is long.
  • the bent CNT 14 a space (gap) is likely to be formed between the surface of the fiber 11 to which the CNT 14 is attached and between the CNTs 14 to which the CNT 14 is attached, and another CNT 14 enters the space. Therefore, by using the bent CNTs 14, the number of CNTs 14 attached to the fibers 11 (the number of CNTs 14 forming the structure 12) is larger than that in the case of using the CNTs having a high linearity.
  • the length of the CNT 14 is preferably in the range of 0.1 ⁇ m or more and 10 ⁇ m or less. If the length of the CNT 14 is 0.1 ⁇ m or more, the CNTs 14 can be entangled with each other to form a structure 12 in direct contact or direct connection, and as described above, the other CNTs 14 can form a structure 12. It is possible to form a space to enter more reliably. Further, when the length of the CNT 14 is 10 ⁇ m or less, the CNT 14 does not adhere across the fibers 11. That is, as described above, the CNT 14 contained in the structure 12 provided in one fiber 11 is not included in the structure 12 provided in the other fiber 11.
  • the length of the CNT 14 is more preferably in the range of 0.2 ⁇ m or more and 5 ⁇ m or less. If the length of the CNT 14 is 0.2 ⁇ m or more, the number of CNTs 14 attached can be increased to make the structure 12 thicker, and if the length is 5 ⁇ m or less, the CNTs 14 aggregate when the CNTs 14 are attached to the fibers 11. It is difficult and easier to disperse evenly. As a result, the CNT 14 adheres to the fiber 11 more uniformly.
  • CNTs having high linearity are mixed as CNTs adhering to the fiber 11 and that CNTs outside the above-mentioned length range are mixed. Even if there is a mixture, for example, the number of CNTs attached to the fibers 11 can be increased by allowing the CNTs having high linearity to enter the space formed by the CNTs 14.
  • the average diameter of CNT14 is preferably in the range of 1 nm or more and 15 nm or less, and more preferably in the range of 3 nm or more and 10 nm or less. If the diameter of the CNT 14 is 15 nm or less, the CNT 14 is highly flexible, easily adheres along the surface of the fiber 11, is easily entangled with other CNTs 14 and fixed to the fiber 11, and further forms the structure 12. It will be more reliable. Further, if it is 10 nm or less, the bond between the CNTs 14 constituting the structure 12 becomes strong.
  • the diameter of the CNT 14 is a value measured using a transmission electron microscope (TEM) photograph.
  • the CNT 14 may be single-layer or multi-layer, but is preferably multi-layer.
  • the number of CNTs 14 attached to the fibers 11 can be increased and the thickness of the structure 12 can be increased as compared with the case where the CNTs having high linearity are used.
  • the structure 12 is formed in which the CNT 14 is woven like a fiber of a non-woven fabric.
  • One of the improved mechanical strengths of secondary products is the improvement of durability against repeated bending.
  • the effect of improving the peel strength due to the presence of the structure 12 and the effect of absorbing mechanical energy by the composite region Therefore, it is considered that the durability against repeated bending is enhanced.
  • This improvement in peel strength and the effect of absorbing mechanical energy are further enhanced as the number of CNTs 14 adhering to the surface of the fiber 11 is increased, so that the durability against repeated bending becomes higher.
  • the composite material 10 having such characteristics is suitable as a spring material such as a coil spring or a leaf spring to which a load is repeatedly applied, and a secondary product containing the composite material 10 is applied to various springs such as a coil spring or a leaf spring. be able to.
  • a secondary product using the composite material 10 for example, a fiber-reinforced molded product
  • the composite regions impregnated with the matrix resin in the structure 12 and cured are fixed to each other to form a crosslinked structure in which the fibers 11 are crosslinked. ..
  • the composite region in which the impregnated matrix resin is cured has a higher hardness than the cured matrix resin alone and has a large elastic limit, that is, high elasticity.
  • the composite region has higher wear resistance than the matrix resin.
  • the crosslinked structure is formed when the distances between the composite materials 10 are close to each other so that the structures 12 come into contact with each other, the larger the thickness of the structure 12, the more advantageous it is in increasing the number of crosslinks. .. Further, when the composite material 10 is made into a woven fabric or bundled like a multifilament, the number of crosslinked portions in which the composite regions are fixed to each other increases, and the effect of the crosslinked structure becomes large.
  • each part of the structure 12 was, for example, a part of the structure 12 on the surface of the fiber 11 adhered to a cellophane tape or the like and peeled off, and remained on the surface of the fiber 11. It can be obtained by measuring the cross section of the structure 12 with SEM or the like.
  • the thickness of the structure 12 is the average of the thicknesses of the structures 12 measured at 10 points in the measurement range so as to cover the measurement range of the predetermined length along the fiber axis direction of the fiber 11 almost evenly. ..
  • the length of the measurement range is, for example, five times the upper limit of the length range of the CNT 14 described above.
  • the number of CNTs 14 attached to the fibers 11 can be evaluated by the thickness of the structure 12.
  • the thickness (average) of the structure 12 obtained as described above is in the range of 10 nm or more and 300 nm or less, preferably in the range of 15 nm or more and 200 nm or less, and more preferably in the range of 50 nm or more and 200 nm or less.
  • the thickness of the structure 12 is 200 nm or less, the impregnation property of the resin between the fibers 11 is better.
  • the fibers 11 constituting the fiber bundle 20 are substantially aligned with each other in the fiber axial directions without being entangled with each other.
  • the fiber axial direction is the axial direction (extended direction) of the fiber 11.
  • the fiber bundle 20 is composed of a plurality of fibers 11.
  • the number of fibers 11 constituting the fiber bundle 20 is not particularly limited, but may be, for example, in the range of 100 or more and 10 million or less.
  • the entanglement of the fibers 11 in the fiber bundle 20 can be evaluated by the degree of disturbance of the fibers 11.
  • the fiber bundle 20 is observed at a constant magnification with a scanning electron microscope (SEM), and a predetermined number (for example, 10) is observed in the observed range (range of a predetermined length of the fiber bundle 20).
  • SEM scanning electron microscope
  • the length of the fiber 11 of the above is measured.
  • the degree of disturbance of the fibers 11 can be evaluated based on the variation in length of the predetermined number of fibers 11 obtained from this measurement result, the difference between the maximum value and the minimum value, and the standard deviation.
  • the fibers 11 are not substantially entangled by measuring the degree of entanglement according to the method for measuring the degree of entanglement in, for example, JIS L1013: 2010 "Chemical fiber filament yarn test method".
  • JIS L1013: 2010 “Chemical fiber filament yarn test method”. The smaller the measured degree of entanglement, the less the fibers 11 are entangled with each other in the fiber bundle 20.
  • the fiber bundle 20 in which the fibers 11 are not substantially entangled with each other or is less entangled with each other can easily open the fibers 11 uniformly.
  • the CNT 14 can be easily adhered uniformly to each fiber 11, and the fiber bundle 20 is uniformly impregnated with the resin, and each of the composite materials 10 contributes to the strength.
  • the fiber bundle 20 is placed in a CNT isolated dispersion (hereinafter, simply referred to as a dispersion) in which the CNT 14 is isolated and dispersed. Immerse and impart mechanical energy to the dispersion.
  • Isolation and dispersion refers to a state in which CNTs 14 are physically separated one by one and dispersed in a dispersion medium without being entangled, and the proportion of aggregates in which two or more CNTs 14 are aggregated in a bundle is 10%. Refers to the following states.
  • the proportion of the aggregate is 10% or more, the aggregation of CNT 14 in the dispersion medium is promoted, and the adhesion of CNT 14 to the fiber 11 is inhibited.
  • the attachment device 21 includes a CNT attachment tank 22, guide rollers 23 to 26, an ultrasonic generator 27, a traveling mechanism (not shown) for traveling the fiber bundle 20 at a constant speed, and the like. Will be done.
  • the dispersion liquid 28 is housed in the CNT attachment tank 22.
  • the ultrasonic generator 27 irradiates the dispersion liquid 28 in the CNT adhering tank 22 with ultrasonic waves from the lower side of the CNT adhering tank 22.
  • the attachment device 21 is continuously supplied with a long fiber bundle 20 (for example, about 100 m) in which the structure 12 is not formed.
  • the supplied fiber bundle 20 is wound around the guide rollers 23 to 26 in order, and travels at a constant speed by the traveling mechanism.
  • the fiber bundle 20 to which the sizing agent is not attached to each fiber 11 is supplied to the bonding device 21.
  • the sizing agent referred to here is attached to the surface of the fiber 11 in order to prevent entanglement of the fiber 11, and is different from the sizing agent and the fixing resin portion described above.
  • the fiber bundle 20 is wound around the guide rollers 23 to 26 in an opened state.
  • the fiber bundle 20 wound around the guide rollers 23 to 26 is less likely to be entangled with the fibers 11 due to the action of an appropriate tension.
  • the winding angle of the fiber bundle 20 around the guide rollers 24 to 26 is preferably smaller (90 ° or less).
  • the guide rollers 23 to 26 are all flat rollers. As shown in FIG. 5, the roller length (length in the axial direction) L1 of the guide roller 23 is sufficiently larger than the width WL of the spread fiber bundle 20.
  • the guide rollers 24 to 26 are the same as the guide rollers 23, and their roller lengths are sufficiently larger than the width WL of the spread fiber bundle 20. For example, the guide rollers 23 to 26 are all the same size.
  • a plurality of fibers 11 are lined up in the thickness direction (diameter direction of the guide roller).
  • the guide rollers 24 and 25 of the guide rollers 23 to 26 are arranged in the CNT attachment tank 22. As a result, between the guide rollers 24 and 25, the fiber bundle 20 runs linearly in the dispersion liquid 28 at a constant depth.
  • the traveling speed of the fiber bundle 20 is preferably in the range of 0.5 m / min or more and 10000 m / min or less.
  • the traveling speed of the fiber bundle 20 is 100 m / min or less, the entanglement of the fibers 11 can be suppressed more effectively and the uniformity of adhesion of the CNT 14 can be further improved.
  • it is more preferable that the traveling speed of the fiber bundle 20 is within the range of 5 m / min or more and 50 m / min or less.
  • the ultrasonic generator 27 applies ultrasonic vibration as mechanical energy to the dispersion liquid 28. This creates a reversible reaction state in which the dispersed state in which the CNTs 14 are dispersed and the aggregated state in which the CNTs 14 are aggregated alternately change in the dispersion liquid 28.
  • the CNT 14 adheres to each fiber 11 by van der Waals force when shifting from the dispersed state to the agglutinated state.
  • the mass of the fiber 11 with respect to the CNT 14 is as large as 100,000 times or more, and the energy for the attached CNT 14 to be detached is larger than the energy due to the ultrasonic vibration.
  • the CNT 14 once attached to the fiber 11 is not peeled off from the fiber 11 even by the ultrasonic vibration after the attachment. Since the masses of the CNTs 14 are extremely small, they alternate between a dispersed state and an aggregated state due to ultrasonic vibration.
  • the frequency of ultrasonic vibration applied to the dispersion liquid 28 is preferably 40 kHz or more and 950 kHz or less.
  • the frequency is 40 kHz or more, the entanglement of the fibers 11 in the fiber bundle 20 is suppressed. Further, when the frequency is 950 kHz or less, the CNT 14 adheres well to the fiber 11.
  • the frequency of ultrasonic vibration is preferably 100 kHz or higher, more preferably 130 kHz or higher. Further, the frequency of ultrasonic vibration is more preferably 430 kHz or less.
  • the number of CNTs 14 adhering to the fibers 11 is almost maximized while ensuring the uniformity of adhesion of the CNTs 14 to the fibers 11 by shifting the CNTs 14 from the dispersed state to the agglomerated state 65,000 times.
  • the maximum value of the number of adhered particles changes depending on the CNT concentration of the dispersion liquid 28, and increases as the CNT concentration of the dispersion liquid 28 increases. However, if the CNT concentration of the dispersion liquid 28 becomes so high that the CNT 17 cannot take a dispersed state when ultrasonic vibration is applied, the CNT 17 cannot be attached to the fiber 11.
  • the length of the period during which the fiber bundle 20 is traveling in the dispersion liquid 28, that is, the time during which the fiber bundle 20 is traveling between the guide rollers 24 and 25 (hereinafter referred to as the immersion time) is applied to the dispersion liquid 28.
  • the traveling speed of the fiber bundle 20 may be 12 m / min or less. Further, even when the fiber bundle 20 is immersed in the dispersion liquid 28 in a plurality of times, the number of adhered CNTs 14 can be substantially maximized if the total immersion time is 65,000 times or more of the period of ultrasonic vibration.
  • a standing wave having a fixed sound pressure (amplitude) distribution is generated in the dispersion liquid 28 in the CNT adhesion tank 22 by the ultrasonic vibration applied from the ultrasonic generator 27. ..
  • the guide rollers 24 and 25 are oriented in the depth direction so that the fiber bundle 20 travels in the dispersion liquid 28 at a depth at which the standing wave node of ultrasonic vibration, that is, the sound pressure is minimized.
  • the position has been adjusted. Therefore, the depth from the liquid surface of the dispersion liquid 28 in which the fiber bundle 20 travels in the dispersion liquid 28 is D, and the wavelengths of the standing waves of the ultrasonic vibration generated in the dispersion liquid 28 are ⁇ and n.
  • the wavelength ⁇ of the standing wave can be obtained based on the speed of sound in the dispersion liquid 28 and the frequency of ultrasonic vibration applied from the ultrasonic generator 27.
  • the depth of the fiber bundle 20 running in the dispersion liquid 28 it is possible to suppress the vibration of the fiber 11 due to the sound pressure and prevent the thread disorder due to the thread slack, and the fibers 11 can be prevented from being disturbed.
  • the fiber 11 is less likely to be stretched in the fiber axis direction due to the sound pressure of the standing wave, and the plastic deformation of the fiber 11 in the fiber axis direction can be prevented.
  • the depth at which the fiber bundle 20 travels in the dispersion liquid 28 may deviate slightly from the node of the standing wave.
  • n ⁇ ⁇ / 2- ⁇ / 8 or more n ⁇ ⁇ / 2 + ⁇ / 8 It is preferably within the following range (n ⁇ ⁇ / 2- ⁇ / 8 ⁇ D ⁇ n ⁇ ⁇ / 2 + ⁇ / 8).
  • the fiber bundle 20 is drawn out of the dispersion liquid 28 and then dried.
  • the sizing agent is applied to the structure 12 by sequentially performing the sizing treatment and the drying on the dried fiber bundle 20.
  • the sizing process can be performed by a general method.
  • the sizing agent is not particularly limited, and various reaction-curable resins, thermosetting resins, and thermoplastic resins can be used as described above.
  • the thermosetting resin include epoxy resin, phenol resin, melamine resin, urea resin (urea resin), unsaturated polyester, alkyd resin, thermosetting polyimide, and resin having a reactive group.
  • the thermoplastic resin include polyethylene, polypropylene, polystyrene, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin, methacrylic resin (PMMA, etc.), general-purpose resin such as vinyl chloride, polyamide, polyacetal, and the like.
  • Examples thereof include engineering plastics such as polyethylene terephthalate, ultrahigh molecular weight polyethylene and polycarbonate, and super engineering plastics such as polyphenylene sulfide, polyether ether ketone, liquid crystal polymer, polytetrafluoroethylene, polyetherimide, polyarylate and polyimide.
  • a resin serving as a sizing agent it is preferable to use a solution in which a resin serving as a sizing agent is dissolved, and it is preferable to apply the solution to the fiber bundle 20 or the like to attach the sizing agent to the CNT 14 of the structure 12.
  • the dispersion liquid 28 used for adhering the CNTs 14 to the composite material 10 is prepared by adding, for example, a long CNT (hereinafter referred to as a material CNT) to the dispersion medium and using a homogenizer, a shearing force, an ultrasonic disperser, or the like to obtain the material CNTs. Is cut to obtain CNT14 having a desired length, and the CNT14 is prepared by making the dispersion uniform.
  • a material CNT hereinafter referred to as a material CNT
  • the dispersion medium examples include alcohols such as water, ethanol, methanol and isopropyl alcohol, and organic substances such as toluene, acetone, tetrahydrofuran (THF), methyl ethyl ketone (MEK), hexane, normal hexane, ethyl ether, xylene, methyl acetate and ethyl acetate.
  • alcohols such as water, ethanol, methanol and isopropyl alcohol
  • organic substances such as toluene, acetone, tetrahydrofuran (THF), methyl ethyl ketone (MEK), hexane, normal hexane, ethyl ether, xylene, methyl acetate and ethyl acetate.
  • THF tetrahydrofuran
  • MEK methyl ethyl ketone
  • hexane normal hexane
  • the material CNT that is the source of the curved CNT 14 is a curved CNT.
  • material CNTs those having the same diameter of individual material CNTs are preferable.
  • An example of the material CNT is shown in the SEM photograph of FIG.
  • the material CNTs are preferably those capable of isolating and dispersing CNTs even if the length of each CNT produced by cutting is large. As a result, a dispersion liquid 28 in which CNT 14 satisfying the above-mentioned length conditions is isolated and dispersed can be easily obtained.
  • the composite material 10 of this example as described above, a bent shape is attached as the CNT 14, so that the composite material 10 is formed between the CNT 14 and the surface of the fiber 11 to which the CNT 14 is attached, between the attached CNTs 14, and the like. Another CNT 14 enters the space. As a result, more CNT 14 adheres to the fiber 11. Further, since the CNT 14 is firmly adhered to the fiber 11 to form the structure 12, the CNT 14 is more difficult to peel off from the fiber 11.
  • the fiber-reinforced molded product produced by using such a composite material 10 has higher CNT-derived characteristics.
  • the secondary product produced by using the composite material 10 as described above has mechanical properties such as vibration damping characteristics (vibration damping property) and elastic modulus change characteristics as compared with the conventional secondary products using the composite material. improves. Regarding the change characteristic of the elastic modulus, the increase in the elastic modulus of the fiber-reinforced molded product is suppressed with respect to the increase in the collision speed with the fiber-reinforced molded product.
  • the concentration of CNT14 in the dispersion liquid 28 is preferably in the range of 0.003 wt% or more and 3 wt% or less.
  • the concentration of CNT 14 in the dispersion liquid 28 is more preferably 0.005 wt% or more and 0.5 wt% or less.
  • the fixing of CNTs to the surface of the fibers is due to the binding of the fibers and CNTs by van der Waals force, but in addition to this, the binding portion that reinforces the fixing of CNTs to the surface of the fibers. May be provided.
  • the binding portion is, for example, an epoxy resin cured in a state of being inserted into a gap formed between each surface (peripheral surface) of the fiber and the CNT directly attached (contacted) to the fiber.
  • the epoxy resin is a fiber bundle containing fibers in which a structure is formed by dissolving it in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), butanol, ethyl acetate or butyl acetate to form a solution. After soaking, heat. As a result, the uncured epoxy resin is allowed to enter the gaps formed between the fibers and the surfaces of the CNTs and cured.
  • a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), butanol, ethyl acetate or butyl acetate.
  • a solution of epoxy resin which is the material of the binding portion, may be emulsified and used.
  • it can be emulsified by adding an emulsifier such as a nonionic emulsifier to a solution in which an epoxy resin is dissolved in a solvent.
  • the binding portion may be, for example, a phenol resin, a polyurethane resin, a melamine resin, a urea resin, a polyimide resin, or the like, in addition to the epoxy resin.
  • a silane coupling agent or an inorganic adhesive can also be used as the binding portion.
  • the composite material of the second embodiment has a plurality of fixing resin portions for partially fixing a part of the plurality of CNTs constituting the structure to the surface of the fiber. Since the composite material of the second embodiment is the same as the composite material of the first embodiment except that a fixing resin portion is provided instead of the sizing agent, substantially the same members are designated by the same reference numerals. Therefore, the detailed description thereof will be omitted.
  • the composite material 10A is provided with a plurality of fixing resin portions 38 for partially fixing a part of the plurality of CNTs 14 constituting the structure 12 to the surface of the fiber 11.
  • the composite material 10A may be a resin-impregnated fiber, or may be used as a single yarn constituting a multifilament or a reinforcing fiber of a fiber-reinforced molded product.
  • the fixed resin portion 38 is obtained by curing the resin into particles that reach the surface of the fiber 11 from the surface of the structure 12.
  • the fixing resin portion 38 is fixed to the surface of the fiber 11 to which the bottom portion is attached, and is also fixed to the CNT 14 of the structure 12 covered by the portion above the bottom portion. In this way, the fixing resin portion 38 fixes the CNT 14 to the fiber 11 by fixing to both the surface of the fiber 11 and a part of the CNT 14.
  • the fixing resin portion 38 partially fixes a part of the plurality of CNTs 14 constituting the structure 12 to the surface of the fiber 11, and is provided so as to be scattered on the surface of the fiber 11. , The CNT 14 of the structure 12 is fixed at each location. The upper portion of the fixed resin portions 38 provided scattered in this way is exposed on the surface of the structure 12, and the fixed resin portions 38 are also scattered and observed on the surface of the structure 12.
  • the fixed resin portion 38 is formed in a range extending from the surface of the structure 12 to the surface of the fiber 11 in the radial direction of the fiber 11 (the thickness direction of the structure 12), and the fiber 11 is formed. It is fixed to the surface of the CNT 14 and is fixed to the portion of the CNT 14 contained therein.
  • the CNT 14 of the structure 12 may have a portion attached to the surface of the fiber 11, a portion overlapping the other CNT 14 or a portion sandwiched therein, which is fixed to the fixing resin portion 38. Further, in some CNTs 14, the end portion and the central portion thereof are fixed to the fixing resin portion 38. In this way, the CNT 14 fixed to the fixing resin portion 38 is strongly fixed to the fiber 11 by the fixing resin portion 38.
  • the portion of the CNT 14 that is not covered with the fixed resin portion 38 adheres to the surface of the fiber 11 by van der Waals force as described above, and therefore has a weaker force than the portion fixed by the fixed resin portion 38. By action, it floats away from the surface of the fiber 11 and can move on the surface of the fiber 11. Further, on the surface of the structure 12, the portion not fixed by the fixing resin portion 38 of the CNT 14 is in a free state in which the portion is separated from the surface of the structure 12 and can be lifted.
  • the partial dropout of the structure 12 is suppressed as compared with the case where the CNT 14 of the structure 12 is not fixed by the fixing resin portion 38.
  • the characteristics derived from the CNT of the fiber-reinforced molded product are further enhanced. Since the CNT 14 of the fixed resin portion 38 is constrained to the surface of the fiber 11, the current from the fiber 11 can be easily passed, which can contribute to the improvement of the conductivity of the fiber reinforced molded product.
  • the CNTs 14 constituting the structure 12 may be fixed to the fibers 11 by the fixing resin portion 38, it is sufficient if some of the CNTs 14 are fixed. That is, at least a part of the CNT 14 constituting the structure 12 may be fixed by the fixing resin portion 38. Since the CNT 14 forms a film as a structure 12 having a non-woven fabric-like structure, the performance can be exhibited as long as at least a part of the CNT 14 constituting the structure 12 is fixed.
  • the number ratio N of the fixed resin portion 38 which is the number per 5 ⁇ m square on the surface (outer peripheral surface) of the structure 12 in a plan view, is preferably in the range of 27 or more and 130 or less. Further, on the surface of the structure 12 viewed in a plan view, the area ratio S of the fixed resin portion 38 is preferably in the range of 6% or more and 45% or less, and the area ratio S is in the range of 7% or more and 30% or less. More preferably.
  • the area ratio S is the ratio of the area where the plurality of fixed resin portions 38 cover the surface of the structure 12 to the surface area of the structure 12 on the surface of the structure 12 in a plan view, and is the ratio of the area of the structure 12 in a predetermined range.
  • S1 is the area where each fixed resin portion 38 within a predetermined range covers the surface of the structure 12.
  • the peripheral surface of the structure 12 is observed in a plane from a direction orthogonal to the fiber axis direction of the fiber 11.
  • the surface of the structure 12 can be regarded as the surface of the fiber 11, and the fixed resin portion 38 is a structure for each fixed resin portion 38.
  • the area covering the surface of the body 12 and the area covering the surface of the fiber 11 can be regarded as substantially the same. Therefore, the number ratio N and the area ratio S are the number ratio, which is the number of fixed resin portions 38 per 5 ⁇ m square on the surface (outer peripheral surface) of the fiber 11 in a plan view, and the fiber 11 on the surface of the fiber 11 in a plan view. It can be regarded as the ratio of the area where the fixed resin portion 38 covers the surface of the fiber 11 to the surface area.
  • the structure 12 formed on the peripheral surface of the fiber 11 is observed in a plane using an SEM photograph. Then, a 5 ⁇ m square observation frame is set on the flat observation image of the structure 12 in the SEM photograph, the number of the fixed resin portions 38 in the observation frame is counted, and the number is defined as the number ratio N. Similarly, the area of each fixed resin portion 38 observed in the observation frame is obtained, and the area ratio S is calculated by assuming that the total area of each of these fixed resin portions 38 is the area S1 and the area of the observation frame is the surface area S2. be able to.
  • the observation frame G is preferably set so that its center of gravity coincides with the radial center of the fiber 11.
  • the CNT 14 can be reliably fixed to the surface of the fiber 11, and the partial shedding of the structure 12 can be reduced. Further, when the number ratio N and the area ratio S are reduced, the portion of the CNT 14 that is not fixed by the fixed resin portion 38 increases, and the degree of freedom of the CNT 14 and the degree of freedom of the structure 12 are increased.
  • the CNT 14 can be reliably fixed to the fiber 11 by the fixing resin portion 38, and the effect of reducing partial dropout of the structure 12 is certain.
  • the properties derived from CNT of the fiber-reinforced molded product are further enhanced.
  • the number ratio N is 130 or less or the area ratio S is 45% or less, the CNT 14 which is entirely covered with the fixed resin portion 38 can be sufficiently reduced.
  • the number ratio N and the area ratio S are preferably within the above ranges at the same time.
  • the area ratio S can be increased or decreased substantially in proportion to the number ratio N, and the number ratio N and the area ratio S can simultaneously satisfy the above conditions.
  • the total area of the fixing resin 38 of 5 ⁇ m in square in the surface, seen in plan view, of the structure 12 it will be in the range of 1.5 ⁇ m 2 ⁇ 11.25 ⁇ m 2.
  • the substantial area of one per fixing resin portion 38 on the surface of the structure 12 it is preferable that the 0.03 .mu.m 2 or 1.12 .mu.m 2 within the following ranges.
  • the individual area of the fixing resin portion 38 is 0.03 ⁇ m 2 or more, a fixing force for securely fixing the CNT 14 to the surface of the fiber 11 can be obtained. In this case as well, the effect of reducing the partial dropout of the structure 12 can be surely obtained.
  • the individual area of the fixed resin portion 38 is 1.12 ⁇ m 2 or less, a sufficient degree of freedom of the CNT 14 can be obtained.
  • the area ratio S and the number ratio N of the fixed resin portion 38 in a plan view and the individual substantial area of the fixed resin portion 38 can be obtained by using image analysis software (for example, Winroof2015 (manufactured by Mitani Corporation)). Can be done.
  • image analysis software for example, Winroof2015 (manufactured by Mitani Corporation)
  • the fiber-reinforced molded product or the like produced from the composite material 10A including the structure 12 composed of the curved CNT 14 is derived from the CNT 14 and has improved characteristics as compared with the conventional one.
  • the elastic modulus of the fiber-reinforced molded product using the composite material 10A is enhanced by the restraining effect of suppressing the displacement of the fiber 11 due to the composite region. Further, in the fiber-reinforced molded product, the increase in the elastic modulus of the fiber-reinforced molded product is suppressed with respect to the increase in the collision speed with the fiber-reinforced molded product due to the restraining effect of the composite region between the fibers. As a result, the velocity dependence of the elastic modulus becomes small. Furthermore, the fixing resin portion 38 can further increase the growth resistance of delamination cracks.
  • the manufacturing process of the composite material 10A is the same as that of the first embodiment except that the fixing resin portion 38 is formed instead of the sizing treatment for adhering the sizing agent to the surface of the structure 12. .. That is, the fixing resin portion 38 is formed by applying the fixing resin to the fiber bundle 20 that has been drawn out from the dispersion liquid 28 (see FIG. 2) and then dried.
  • the fixing resin applying treatment can be a treatment according to the material to be the fixing resin portion 38 and its form.
  • the fixing resin applying treatment there is a method of using an emulsion type treatment liquid in which an uncured resin (polymer) to be a fixing resin portion 38 is dispersed in droplet form as a dispersion medium.
  • an emulsion type treatment liquid in which an uncured resin (polymer) to be a fixing resin portion 38 is dispersed in droplet form as a dispersion medium.
  • the fiber bundle 20 in which the structure 12 is formed on each fiber 11 is opened and brought into contact with the treatment liquid to attach the resin to the fiber bundle 20, and the dispersion medium is evaporated after the adhesion treatment.
  • the curing treatment of curing the resin to form the fixed resin portion 38 is sequentially performed.
  • a resin having a curable property that is, a curable resin
  • the curable resin may be any of a thermosetting resin, a reaction curable resin and the like.
  • the cured resin obtained by curing the curable resin may be a thermoplastic resin. Specific examples thereof include epoxy resin, urethane resin, urea resin, polyimide resin, vinyl acetate, acrylic resin, olefin resin, vinyl chloride, phenol resin, melamine resin, rubber-based resin, silicon-based resin and inorganic adhesive. However, it is not limited to these.
  • the fixed resin portion 38 preferably has a high affinity with the matrix resin. Therefore, it is preferable that the fixed resin portion 38 and the matrix resin are, for example, a combination of polar resins or a combination of non-polar resins.
  • dispersion medium of the treatment liquid examples include water, ethanol, acetone, MEK, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, toluene and xylene. These dispersion media may be used alone or in combination of two or more. As the dispersion medium, water is preferable from the viewpoint of handleability and safety.
  • concentration of the resin in the treatment liquid after dilution is appropriately adjusted so as to be the amount of adhesion of the target fixed resin portion 38 (ratio of the mass of the fixed resin portion 38 to the composite material 10A (wt%)).
  • the amount of the fixed resin portion 38 adhered to the surface of the fiber 11 after the drying treatment is preferably in the range of 0.1 wt% or more and 5.0 wt% or less, more preferably in the range of 0.3 wt% or more and 3.0 wt% or less. Is.
  • the particle size of the resin in the treatment liquid is preferably in the range of 0.05 ⁇ m or more and 1 ⁇ m or less, and more preferably in the range of 0.1 ⁇ m or more and 0.4 ⁇ m or less.
  • the particle size of the resin in the treatment liquid can be determined by a laser analysis method. If the particle size of the resin in the treatment liquid is 0.05 ⁇ m or more, the CNT 14 can be reliably fixed to the surface of the fiber 11, and if it is 1 ⁇ m or less, the resin can be reliably fixed between the CNTs 14 constituting the structure 12. It can enter and can surely prevent the CNT 14 from being covered with the resin. Further, if it is 0.1 ⁇ m or more, the resin size is sufficient for fixing the non-woven fabric-like structure 12, and if it is 0.4 ⁇ m or less, the structure 12 can be partially fixed.
  • the particle diameter using an emulsion type of processing liquid containing 0.4 ⁇ m or less in the range of resins than 0.1 [mu] m fixed resin portion 38 within each area of 0.03 .mu.m 2 or 1.12 .mu.m 2 or less Can be formed.
  • the number ratio N is set to be within the range of 27 or more and 130 or less. can do.
  • the method of adhesion treatment using the treatment liquid is not particularly limited, and examples thereof include a roller immersion method, a roller contact method, and a spray method.
  • the curing treatment method is not particularly limited, and for example, hot air, a hot plate, a heating roller, various infrared heaters, and the like can be used.
  • FIG. 10 shows a flat belt 40 as an example of a product using the composite material 10.
  • the flat belt 40 is used as, for example, a power transmission belt or the like.
  • the flat belt 40 has a structure in which a reinforcing cloth 42 and a surface rubber layer 43 are laminated on both sides of the internal rubber layer 41, respectively, and a cord core wire 45 is embedded in the internal rubber layer 41.
  • the inner rubber layer 41 is made of, for example, nitrile rubber, carboxylated nitrile rubber, hydrogenated nitrile rubber, chloroprene rubber, chlorosulphonized polyethylene, polybutadiene rubber, natural rubber, EPM, EPDM, urethane rubber, acrylic rubber and the like. ..
  • the reinforcing cloth 42 is provided to improve the durability of the flat belt 40, and for example, woven or knitted cloth such as polyester fiber, nylon fiber, aramid fiber, glass fiber, carbon fiber, and cotton is used.
  • the surface rubber layer 43 is provided to obtain a predetermined frictional force between the flat belt 40 and the conveyed object or power transmission device, and is, for example, a nitrile rubber, a carboxylated nitrile rubber, a hydrogenated nitrile rubber, a chloroprene rubber, or a chlorosulphon. It is made of polyethylene chemical, polybutadiene rubber, natural rubber, EPM, EPDM, urethane rubber, acrylic rubber, silicon rubber and the like.
  • the cord core wire 45 As the cord core wire 45, the above-mentioned multifilament 15 in which the composite materials 10 are bonded to each other by the matrix resin 16 impregnated into the structure 12 and cured is used.
  • the cord core wire 45 has a fiber axis direction of the multifilament 15 and a longitudinal direction of the flat belt 40 (running direction of the flat belt 40, arrow X direction) coincident with each other. Further, the cord core wires 45 are arranged at a predetermined pitch in the width direction orthogonal to the longitudinal direction of the flat belt 40.
  • a twisted multifilament is used as the cord core wire 45, it is preferable to alternately arrange the S-twisted one and the Z-twisted one in order to suppress the skew of the belt.
  • the flat belt 40 since the flat belt 40 uses the multifilament made of the composite material 10 as the cord core wire 45, the flat belt 40 has a small elongation with respect to tension and compression, and has high durability against repeated bending.
  • a composite material can be used as a cord core wire of various belts, and in particular, the composite material is a toothed belt represented by a timing belt, a V-belt, a V-ribbed belt, or the like. It is suitable as a cord core wire of a transmission belt.
  • the example shown in FIG. 11 uses the multifilament 15 as the cord core wire 45 of the V-belt 50
  • the example shown in FIG. 12 uses the multifilament 15 as the cord core wire 45 of the timing belt 60. is there.
  • the timing belt 60 of FIG. 12 has a rubber layer 61 composed of a belt main body portion 61a and a plurality of tooth portions 61b, and a tooth cloth 62 covering the surface of the rubber layer 61 on the tooth portion 61b side, and the belt main body. It has a structure in which the cord core wire 45 is embedded in the portion 61a.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Reinforced Plastic Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne : un matériau composite qui permet d'améliorer davantage les caractéristiques dérivées de nanotubes de carbone qui sont attachés à des fibres ; et un procédé de production du matériau composite. Un matériau composite 10 dans lequel des structures 12 qui sont formées à partir d'une pluralité de nanotubes 14 de carbone sont formées sur les surfaces de fibres. Les nanotubes de carbone 14 sont courbés. Les nanotubes de carbone 14 sont fixés aux surfaces des fibres 11, qui sont des surfaces incurvées, dans diverses postures, et d'autres nanotubes de carbone 14 entrent dans des espaces (intervalles) qui sont formés entre les nanotubes de carbone 14 et les surfaces des fibres 11 et entre les nanotubes de carbone 14 fixés, permettant aux structures 12 d'être formées à partir de davantage de nanotubes de carbone 14.
PCT/JP2020/042901 2019-11-20 2020-11-18 Matériau composite et son procédé de production WO2021100735A1 (fr)

Priority Applications (7)

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US17/778,164 US20230019296A1 (en) 2019-11-20 2020-11-20 Composite material and method for producing same
CN202080079115.8A CN114729499A (zh) 2019-11-20 2020-11-20 复合材料及其制造方法
EP20891341.8A EP4063559A4 (fr) 2019-11-20 2020-11-20 Matériau composite et son procédé de production
KR1020227020334A KR20220093248A (ko) 2019-11-20 2020-11-20 복합 소재 및 그 제조 방법
JP2021558473A JPWO2021100859A1 (fr) 2019-11-20 2020-11-20
TW109140794A TW202124808A (zh) 2019-11-20 2020-11-20 複合材料及其製造方法
PCT/JP2020/043412 WO2021100859A1 (fr) 2019-11-20 2020-11-20 Matériau composite et son procédé de production

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TWI767811B (zh) * 2021-07-30 2022-06-11 臺灣塑膠工業股份有限公司 碳纖維束的處理方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008201626A (ja) * 2007-02-20 2008-09-04 Toray Ind Inc カーボンナノチューブ集合体、その製造方法
JP2016194165A (ja) * 2015-03-31 2016-11-17 ニッタ株式会社 複合素材の製造方法および複合素材
US20180230634A1 (en) * 2015-08-08 2018-08-16 Himalibahen K. VYAS Apparatus for textile processing and method of manufacturing

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008201626A (ja) * 2007-02-20 2008-09-04 Toray Ind Inc カーボンナノチューブ集合体、その製造方法
JP2016194165A (ja) * 2015-03-31 2016-11-17 ニッタ株式会社 複合素材の製造方法および複合素材
US20180230634A1 (en) * 2015-08-08 2018-08-16 Himalibahen K. VYAS Apparatus for textile processing and method of manufacturing

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